High performance polymers for oil and gas applications

Al Christopher C. de Leon a, Ítalo G.M. da Silva a, b, Katrina D. Pangilinan a, d, Qiyi Chen a, c,

Eugene B. Caldona a, d, Rigoberto C. Advincula a, c, d,*
a
Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH 44106, USA
b
Escola de Química, Universidade Federal do Rio de Janeiro, Rio de Janeiro, RJ 21941-909, Brazil
c
Oak Ridge National Laboratory, Center for Nanophase Materials and Sciences, Oak Ridge, TN 37830, USA
d
Department of Chemical and Biomolecular Engineering and Joint Institute for Advanced Materials, University of Tennessee, Knoxville, TN 37996, USA

Abstract
Proper material selection has been one of the most important aspects in the design of chemical process
equipment. In particular, the oil and gas industry has transitioned from using metals to non-metals (e.g.
advanced and high performance polymeric materials) in most of their structural components, coatings,
equipment parts, and the like. It is therefore imperative to understand the advantages and limitations of these
polymer materials before they can be effectively used for a specific application. This review article aims to
provide an overview of the properties, applications, and durability against reactivity and degradation of high-
performance polymers commonly used in the oil and gas industry. These include polysulfone, polyetherimide,
polyphenylene sulfide, polyetheretherketone, fluoropolymers, and other high performance thermosets,
elastomers, and polymer nanocomposites. This article also covers the current research efforts in improving the
properties of high-performance polymers and expanding their applications (including 3D printing or additive
manufacturing) in the oil and gas industry.

Acknowledgments

This study was supported in part by the Coordenação de Aperfei- çoamento de Pessoal de Nível Superior - Brasil
(CAPES) - Finance Code 001 for Italo da Silva. Work (or Part of this work) was conducted at ORNL’s Center for
Nanophase Materials Sciences by R.C.A. which is a US Department of Energy Office of Science User Facility. RCA also
ac- knowledges funding from the Governor’s Chair program, the University of Tennessee.
Introduction

Improper choice of materials in chemical industries can pose, not only serious economic issues, but also potential hazards and
accidents, which can put peoples’ lives at risk. A vast number of reports and safety audits describe accidents that could have been
prevented had proper structural materials and coatings been used and maintained. The Bureau of Safety and Environmental
Enforcement (BSEE) and the Occupational Safety and Health Administration (OSHA) reported different accidents that can be traced
from misuse of materials. Fire is often the result of material failure due to corrosion of unprotected metallic parts, or use of non-
metallic materials that are unable to withstand high temperature conditions. BSEE compiled all the incidents associated specifically
with oil and gas operations [1–3].

Shell Offshore, Inc., for example, had different fire incidents resulting from failure of non-metallic materials. In 1997, a
transformer shortage caused a cured coating to melt into a high temperature liquid, subsequently causing fire. In 1999, a small fire
also occurred due to failure of seals, causing friction and excessive high temperature buildup, eventually igniting the surrounding
lubricant. Vastar Resources, Inc. incurred a similar incident due to failure of an O-ring, where a metal-to- metal friction and oil leak
from the pump caused a fire. BSEE also reported that Exxon Corporation had an accident involving a corroded saltwater relief
valve, in which salt water was sprayed into a high-voltage panel, causing its electrical system to short out.

Accidents due to improper material use occur, not only in oil and gas industries, but also in other giant chemical and
manufacturing industries, as in the case for the incident in 2009 at NDK Crystal, Inc. in Belvidere (IL, USA) [4]. NDK manufactures
synthetic quartz via recrystallization of raw mined quartz in NaOH solution containing small amounts of LiNO3 in a 14-m long
steel alloy cylindrical vessel (see Fig. 1a). This process, known as hydrothermal synthesis, simulates the natural geologic
crystal growth through high temperature (371 ◦C) and high pressure (200 MPa) operations. During this process, the direct
exposure of steel vessel to NaOH solution and silica resulted in the formation of acmite (sodium iron silicate), which served as a
protectivecoating for the steel vessel wall. However, on December 7, 2009, one of the steel vessels was violently ruptured, bursting a
superheated liquid with steel vessel fragments flying over a distance of 250 m in all directions, damaging the product storage area,
laboratory, and production offices, and fatally injuring an individual (Fig. 1b). Further investigations revealed that the probable
cause of the vessel rupture was stress corrosion cracking as a result of simultaneous effects of pressure and the corrosive
environment. Such incident could have been pre- vented had the inner wall of the steel vessel been coated with a high performance
coating that can withstand high temperature, high pressure, and chemical attack.

Another accident resulting from improper choice of material was the fatal exposure of a veteran operator to a highly toxic
phosgene in a DuPont facility (Belle, WV, USA) in 2010 [5]. Inhaled phosgene undergoes hydrolysis and forms HCl, which irritates
the upper respiratory system. It can also react with the proteins in the pulmonary bronchioles and alveoli, resulting in the
disruption of the blood-air barrier and subsequent accumulation of liquid in the lungs. At DuPont, phosgene is used as a raw
material for the production of their chemical products. A stainless steel braided hose with a material lining is used to transfer the
phosgene from the storage tank to the processing equipment. On January 23, 2010, the steel hose suddenly failed, causing roughly
1 kg of phosgene to be sprayed over the chest and face of an operator, who was, at that time, inspecting the phosgene cylinders (Fig.
2). The operator was rushed to the hospital, but unfortunately died the following night. Post-incident inspection of the steel hose
revealed that the failure was caused by a corrosion localized underneath an adhesive tape used to secure the manufacturer’s tag.
The phosgene vapor diffuses through the permeable lining and hydrolyzes beneath the adhesive, eventually corroding the
underlying stainless steel. Such incident could have been prevented had proper hose material been used.

It is of utmost priority for industrial companies to keep their employees, contractors and the public safe at all times. It is
also extremely important to acquire a thorough understanding of the material properties, stability, and durability prior to their
utility as protective coatings or structural parts. Furthermore, the various safety hazards resulting in accidents in big industrial
corporations, which often have well-funded safety departments, represent a major problem in their comprehensive risk assessment
and lack of mitigation plans. Such shortcomings can even be more aggravated in third world countries, where entities like BSEE
and OSHA are either less active, or do not even exist at all [6].

High performance polymers (HPPs) are endowed with the ability to endure extreme weathering conditions, harsh environments,
and mechanical abuse, without compromising their functionality and desirable properties [7]. Due to their excellent characteristics,
HPPs are the most sought-after materials in the industry including the aerospace, medical, marine, chemical, and many more. In
particular, HPPs lead the choice for utility in the oil and gas industry where high heat conditions, material strength, corrosive
environment, and most importantly, high industrial safety levels are the decisive factors. Our group has reviewed different
applications of polymers for the oil and gas industry in the literature: corrosion inhibitors [8], smart cements and additives [9],
stimuli-responsive materials [10], and 3D printed materials - mechanical characterization [11], and applications in membrane
separation, desalination, and water treatment [12]. In this current review, we aim to cover different HPPs, their chemical and
physical properties, and relevance to the oil and gas industry, with highlights on their specific uses, performance, and industrial
safety benefits. We also provide an overview of their utility and durability in high temperature, high pressure, and highly corrosive
applications. Further, we present short contemporary research efforts on the application of several HPPs, which can be potentially
expounded into individual full length review. Note that these discussions are kept short as they are solely intended to pro- vide
brief insights on the current direction and utility of HPPs, while overall maintaining a coherent HPP review.

Polymer classification
Polymers can be classified according to their chemical structure, property, or use. The most common way is classifying them as
thermo- plastics, thermosets, or elastomers. Thermoplastics soften when heated and return to their original condition when cooled.
This process occurs because their polymeric structures are only held together by weak intermolecular forces, which can easily be
disrupted thermally. Ther- mosets, on the other hand, are characterized by cross-linked, three- dimensional network systems, and
do not soften when heated because their backbones are interconnected covalently by a crosslinker, making them difficult to be
reshaped by heating. Lastly, elastomers are stretchable polymers capable of returning to their original shape upon release of an
applied stress. They are characterized by a widely-meshed crosslinked molecular chains that provide the material a high level of
dimensional stability, while being elastic during the application of stress. Similar to thermosets, crosslinked elastomers cannot be
remelted or reshaped [13,14].

According to their temperature, chemical, and mechanical stability (Fig. 3), polymers can also be classified as standard,
engineering, or high performance polymers (HPP). Standard (or commodity) polymers exhibit low mechanical properties and
can only be used at temperatures below 100 ◦C, examples of which are polystyrene (PS), polyvinyl chloride (PVC),
polypropylene (PP), and polyethylene (PE). They are typically produced in large volumes and used in a wide range of low-
temperature applications such as packaging films, containers, clothing, and others where mechanical properties are less important.
Engineering polymers display better mechanical and thermal properties than standard polymers, and can be used at
temperatures between 100 and 150 ◦C. Due to their high-cost, they are consumed in low-volume applications. Examples of
engineering polymers are polyoxymethylenes (POM), polycarbonates (PC), and polyamides (PA). Applications of engineering
polymers include structural parts, motorcycle helmets, ski boots, car bumpers, and the like. HPPs, on the other hand, are polymers
used in applications with higher-level requirements than those for standard and engineering polymers as they are characterized by
superior mechanical properties, outstanding chemical stability, and exceptional thermal stability. This class of polymers will be
discussed in detail in the next section. Examples of HPPs include: amorphous polymers such as polysulfone (PSU) and
polyetherimide (PEI); semi-crystalline polymers like polyphenylene sulfide (PPS) and polyetheretherketone (PEEK); liquid
crystalline polymers; fluoropolymers; and other high- performance polymer composites.

High performance polymers (HPP)

High performance polymers (HPPs) are defined as polymers that can withstand harsh conditions (corrosive environments, high
temperature and pressure conditions, etc.), while retaining their desirable properties. They have been termed as high temperature
polymers, advanced engineering materials, and heat-resistant polymers. There are several required criteria for a polymer to be
considered as high performance. Some of these are listed as follows [7]:

• The polymer durability should at least be 10,000 h at 177 ◦C. At this temperature, the polymer should be able to retain its
properties after short- and long-term exposures to mechanical stress, aggressive chemicals, and electrical shock. The
polymer should also be stable enough at this temperature, while being exposed to different kinds of radiation, and
corrosive environments.
• Thermal decomposition temperature should be a minimum of 450 ◦C. At this temperature, a 5% weight loss is desirable
as measured by dynamic thermogravimetric analysis at a heating rate of 2.5 ◦C min-1
• Minimal weight loss rates at elevated temperatures.
• The temperature at which 10% deflection under 1.52 MPa load occurs should be a minimum of 177 ◦C.
• Polymers with high aromatic content and relatively rigid segments should exhibit high glass transition temperatures (Tg)
and outstanding mechanical properties.

The interest in developing HPPs for the oil and gas industries is driven by the increasing need for materials with outstanding
mechanical, dimensional, and chemical stability at high temperatures and pressures. The high costs associated with the drilling and
production operations, as well as the harsh conditions imposed, especially by off- shore locations, require materials that offer
outstanding stability and durability [15]. The successful development of HPPs requires careful design of the polymer on the
molecular level. The most important factor is the bond strength, quantified by the bond dissociation energy. It is defined as the
amount of energy needed to break a chemical bond. For example, the bond energies of C–C, C–C, C–H, and C–F bonds are 83,
145, 99, and 123 kcal mol-1, respectively. Higher energy is required to break a C–C than a C–C bond; thus, the reason why most
HPPs contain C–C bonds across their backbones. Similarly, fluorinated polymers (polymers containing C–F bonds) are
expected to have higher thermal stability than their non-fluorinated equivalents (specifically those with C–H bonds). Thermal
stability can be further improved by replacing aliphatic with aromatic units, which provide resonance stabilization. It is
estimated that incorporating resonance-stabilized units adds 40–70 kcal mol-1 of bond strength [7]. Subjecting the polymers
to high temperatures does not result in the production of volatile fragments because it is harder to break the resonance-stabilized
bonds. Aside from enhancing the thermal stability, having resonance-stabilized units also improves the chemical resistance of these
polymers. At high temperatures, radical species are produced at the onset of polymer degradation. These radical species then react
with the polymer chain and subsequently break it. If these radical species are generated from the reso- nance stabilized units,
however, they can be less reactive as the π electrons are delocalized within the structure. Therefore, the replace- ment of aliphatic
with aromatic units, not only improves the bond strength of the polymer chain, but also improves its resistance against the
attack of radical species [13].
 The problems with having relatively high aromatic content are increased chain stiffness and decreased polymer
processability. To overcome these shortcomings, heteroatoms (N, O, S, etc.) are introduced to the aromatic units. Although the
resulting polymer will acquire relatively lower thermal stabilities brought about by the overall decrease in the bond
dissociation energy (e.g. bond energies of C–N, C–O, and C–S are 73, 85.5, and 62 kcal mol-1, respectively), the
resulting increase in processability widens the range of their applications. To offset the reduced bond strength, the polymers are
designed to possess, aside from resonance stabilization, secondary forces such as hydrogen bonding, polar interaction, and other
Van der Waals forces all of which can significantly increase the intermolecular chain attraction and improve the thermal
stability of the resulting HPP. Other factors known to improve a polymer’s thermal stability are molecular crosslinking density,
crystallinity, and the additives and reinforcements [13].

Examples of HPPs

Amorphous HHPs

Amorphous polymers are macromolecules that are oriented randomly and do not exhibit short- and long-range order. The
random orientation of the chains results in entangled structures with lack of degree of crystallinity (often detected by X-ray
diffraction and scattering experiments) [14]. Examples of commodity amorphous polymers include polystyrene (PS), poly(vinyl
chloride) (PVC), poly(methyl methacrylate) (PMMA), acrylonitrile butadiene styrene (ABS) polymer, polycarbonate (PC), and
polypropylene carbonate (PPC). On the other hand, high performance amorphous polymers include polysulfone (PSU),
polyetherimide ESU), and poly- phenylsulfone (PPSU).

Polysulpone.

Polysulfone (PSU) is a family of amorphous HPPs that contains sub- unit aryl-SO2-aryl (sulfone) in its backbone. The first
commercial PSU, poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene(1-methylethylidene)-1,4-phenylene) or
bisphenol A polysulfone, was made available by Union Carbide (now a wholly owned subsidiary of the Dow Chemical Company) in
1965. Among all the melt-processable polymers, PSU has one of the highest service temperatures. Its Tg is -185 ◦C, and it is known
to retain its mechanical property from -100 up to 150 ◦C. It is highly resistant to mineral acids, alkali, electrolytes,
oxidizing agents, surfactants, and hydrocarbon oils. They are also resistant against gamma and electron beam radiation.
However, it has low resistance against non-polar to low-polar organic solvents such as dichloromethane, chloroform,
acetone, and aromatic hydrocarbons. Typical properties of PSU are shown in Table 1 [16].

Mechanically, PSU has very high impact resistance and very high flexural modulus brought about by the presence of polar
groups in its chains. It also has a very good dimensional stability even in the presence of hot air, steam, or boiling water. The
exceptionally high-temperature hydrolytic stability of PSU allows its use in medical applications involving autoclave and steam
sterilization. It also has good insulating properties and has been used as insulation for electrical cables and as a circuit board
material, besides automotive applications, sporting goods, uses include wastewater recovery, food and ocessing, and gas separation
[28].

In the oil and gas industry, PSU has been used as an integral part of many commercially available in-line flow meters and
rotameters for oil and petroleum fluid flowrate measurements [29]. Fluid flow rates require close monitoring and accurate
measurements. Use of flow meters made of low-class materials can cause sudden unnoticeable malfunctions when damaged,
which may further affect the product quality, lower the process efficiency, and introduce damages to the machines. Compared to
PVC flow meters, flow meters made of PSU are guaranteed to be continuously usable at higher temperatures and pressures, and
highly corrosive environments. PSU-based flow meters have been successfully commercialized and known to be resistant against
corrosion and prevent scale buildup, which can result in clogging, operation failure, and possibly a minor safety incident issue. PSU
has also been employed as membrane separation material (usually coated with silicone elastomer layer for protection) for hollow-
fiber separators used to separate H2 from NH3 and refinery gases. Compared to other membrane separation materials, commercially
available PSU membranes display better permeability, higher fouling resistance, and can withstand temperatures of up to
120◦C. Solvay Plastics sells their PSU under the tradename Udel® [30]. It is used as fittings, water treatment mem- branes,
faucet cartridges, trocar handles, hemodialysis membranes, and heart valve holders. BASF markets Ultrason® as a transparent, high
temperature amorphous thermoplastic that can be used as membranes and sensors [31].

Current research efforts are also focused on improving the performance of PSU-based filtration membranes for water treatment
and hydrocarbon purification during oil and gas production. Mollahosseini et al. coated PSU with TiO2 nanoparticles and
subsequently polyamide by interfacial polymerization of m-phenylenediamine and trimesoyl chloride [32]. Results showed that the
NaCl rejection of the resulting nanofiltration membrane increased from 70% to 84% compared to the uncoated nanofiltration
membrane. Moreover, the modified nano- filtration membrane showed improved anti-fouling and anti-bacterial property brought
about by the photocatalytic activity of TiO2. Poly (amide-imide) (PAI) and TiO2 nanoparticles were also demonstrated to improve
the performance of PSU membranes [33]. The resulting membrane showed enhancement in pure water flux, porosity,
hydrophilicity, separation efficiency, and anti-fouling properties (Fig. 4).

Gong et al. improved the performance of PSU ultrafiltration membrane by depositing an organosilica layer on it [34]. It has
been shown that by using 1,2-bis(triethoxysilyl)ethane as the precursor, PSU ultra- filtration membrane can be coated with a
uniform, defect-free, and perm-selective layer. The resulting membrane showed a high isopropanol-water (90/10 wt%) separation
factor compared to no selectivity for a PSU ultrafiltration membrane. The membrane also showed long-term stability, improved gas
separation performance, and a moderate separation factor for H2/N2. Modified PSU has also been used to remove sulfur from
gasoline. In a study conducted by Xia and co-workers, CuO-filled aminomethylated PSU hybrid membrane was used to separate
n-heptane and thiophene [35]. Permeation flux was measured 23.9 kg μm m-2 h-1, and a sulfur-enrichment factor of 3.9 was
achieved. The investigation of the effect of CuO loading showed an initial increase in the sulfur-enhancement factor, followed
by a decrease with increasing CuO loading. The sulfur-enrichment factor again increased when the CuO loading reached 8 wt%.

Polyetherimide.

The development of polyetherimide (PEI) is driven by the desire to obtain a material exhibiting the thermal and chemical
stability of aromatic ether and imide, while still being melt-processable. Introduced in 1982, PEI was developed by a team headed by
J. Wirth of General Electric’s Center of Research and Development in Schenectady (NY, USA) under the trade name ULTEM® [36].
The synthesis of PEI involves the melt polycondensation of bisphenol A dianhydride with a diamine (usually m-phenylenediamine).
Typical properties of PEI are shown in Table 2. [37]

PEI is known to display outstanding elevated thermal resistance, high strength and stiffness, dimensional stability, and creep
resistance, all of which allow PEI to replace metals and other materials in many structural applications. PEI can be continuously
used at temperatures of up to 180 ◦C and shows excellent hydrolytic stability. It is also known to possess inherent flame-retardant
property, very low smoke emission, and good chemical resistance. In particular, PEI is resistant to hydro- carbons, alcohols, and
halogenated solvents. PEI has found applications in medical and healthcare, electrical/electronics, automotive, aero- space,
pharmaceuticals, metal replacements, bearings, and structural parts. The main disadvantages of using PEI, however, are its notch
sensitivity, high processing temperature requirement, and high material processing costs [36,38].

In the oil and gas industry, PEI-based materials find different applications from drilling to production mainly as membrane
materials. PEI- based carbon hollow fiber membranes have been used in CO 2/CH4 and CO2/N2 separation during natural gas
purification and flue gas treatment processes. Proper selection of gas membrane materials is crucial to the oil and gas industry in
achieving higher separation efficiency, permeability, and selectivity. PEI-based membranes have been successfully commercialized
and are among the gas membrane materials that exhibit the highest selectivity [39]. Commercial PEI membranes have also been
used as porous polymer supports for biofilms during polycyclic aromatic hydrocarbon removal from coking wastewater.These PEI-
based membranes are more advantageous in terms of immobilizing microorganisms than the commonly used suspension-reactors
and solid-bed reactors containing granulated materials. Currently, PEI fiber is also being used in high-end work wear and protective
coating [40]. The utility of PEI in these applications is brought about by its flexibility, softness, and colorable fiber that provides
superior comfort and aesthetics. Most importantly, PEI is chosen due its high heat resistance, inherent flame retardancy, and self-
extinguishing ability in an open flame, providing the possible highest level of safety for workers exposed to harsh and fire-prone
environments in the oil and gas industry. Further, its low smoke emission [37] minimizes the impact of industrial indoor air
pollution on human health. Currently, Sabic sells PEI resins (ULTEM), which offers outstanding thermal resistance, strength,
stiffness, and chemical resistance. In upstream applications, PEI has been used for insulators, spacers, connectors, and structural
parts [41]. Also, RTP company markets the RTP 2100 series of PEI compounds. Their material has been used in marine and
industrial cleats, probe housing, duct assembly, coil spring, and cable guard, and digital card printer frame [42].

Efforts have been made to improve the separation performance of PEI membranes. Duan et al. demonstrated that the gas
permeability can be increased while the ideal selectivity of CO2/N2 and CO2/CH4 are unchanged when a metal organic framework
(Cu3(BTC)2) is incorpo- rated into the PEI membrane [43]. It has been reported that the CO2 permeability is enhanced because
of the increase in its diffusivity, while the N2 benefits from the increase in its solubility. The structure-property relationship of gas
separation membranes made with PEI, as well as other polyimides, was recently reviewed in the literature [44]. Nano- composite
asymmetric films have also been prepared from PEI and palladium acetate [45]. Palladium acetate was converted into
palladium nanoparticles by annealing at 220 ◦C or by chemical treatment, the former being more efficient. The resulting
membrane showed to enhance H2 and CO2 diffusion rates, while maintaining the H2/CO2 selectivity. Hao et al., on the other
hand, showed that the incorporation of soluble polymer of intrinsic microporosity (or PIM-1) into the PEI membrane
significantly increases the permeation rate of gases such as He, N2, O2, CH4, and CO2 without compromising the gas pair
selectivity [46]. They also demonstrated that by adding a small amount of PIM-1, the permeability of CO2 can be increased
from 47% to 167%.

Another area of interest is the fabrication of antistatic PEI matrix nanocomposite. An effective approach to avoid the
accumulation of static electricity in insulated polymer is to incorporate nanofillers that can act as electrostatic discharge
channels. Wang and coworkers fabricated an antistatic PEI by introducing carbon nanotubes (CNTs) and silver nanoparticles
[47]. Electrostatic discharge channels were constructed by the dispersed CNTs and further enhanced by the inclusion of silver
nanoparticles, as evidenced by a significantly higher volume conductivity than that of the pristine PEI or carbon nanotube-loaded
PEI (Fig. 5).

The anticorrosion properties of PEI coatings for magnesium alloys were also evaluated [48]. Dopamine, a biologically
inspired compound that easily self-polymerizes to polydopamine (PDA), was used as an intermediate layer for PEI deposition,
resulting in a very robust hybrid coating (Fig. 6a). Electrochemical tests revealed that the PDA/PEI coating showed superior
corrosion inhibition even after 35 d of immersion in NaCl solution, over the bare and PDA-coated substrates. In agreement with
SEM observations, AFM images revealed a smooth and homogeneous surface for the PDA/PEI coating, corroborated by a
remarkably lower surface roughness (Ra) value (Fig. 6b-d).

Semi-crytalline HPPs.

Semi-crystalline polymers are composed of ordered and amorphous regions. Increasing the temperature does not soften semi-
crystalline polymers, but rather melts after a certain amount of heat is absorbed. Examples of commodity semi-crystalline polymers
include polyethylene (PE) and polyethylene terephthalate (PET), while, examples of high performance semi-crystalline polymers
include polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polyetherketone (PEK), poly-phthalamide (PPA),
polyetherketoneketone (PEKK), poly-aryletherketone (PAEK), thermoplastic polyimide (TPI), and high-temperature nylon (HTN).

Polyphenylene sulfide.

Polyphenylene sulfide (PPS) belongs to a family of polymers known as poly(arylene sulfides), consisting of repeat aromatic
rings joined by sulfur bridges. PPS, in particular, is a semi-crystalline polymer that has recurring p-substituted benzene rings
connected by sulfur atoms. The first commercially available PPS, developed by Edmonds and Hill in 1963, was produced from
dihalogenated aromatics using Na2S in a polar aprotic solvent. Phillips Petroleum (merged with Conoco, Inc. and later became
ConocoPhillips) first produced PPS (under the trademark Ryton, which now belongs to Solvay) in an industrial scale in 1972 [49].
PPS is an outstanding corrosion-resistant coating due to its inertness toward steam, organic solvents, inorganic salts, bleaches, and
strong bases. Aside from its excellent chemical resistance, PPS is also known for its thermal stability, dimensional stability, and its
resistance to mildew, aging, sunlight, and abrasion. Typical properties of PPS are shown in Table 3 [50].

Other interesting properties of PPS include very low coefficient of friction, electrical conductivity, good wear resistance,
flame retardancy, and good creep resistance. When melted, PPS exhibits low viscosity, which permits high loading of fillers and
reinforcements. PPS has also been used in business, medical, and healthcare equipment and as automotive, engineering, pump, and
gear components, and metal re- placements. However, the need for very high processing temperature (melt temperature) and its
comparatively high cost, brittleness and susceptibility to warpage limit its applications. The brittleness can be overcome, however,
by reinforcement with fibers and fillers [49,51].

Due to its excellent balance of properties, PPS is used in the oil and gas industry commercially as fillers to improve the
extrusion and deformation resistance of PTFE, which is mostly used in sealing liquid natural gas and coating heat exchangers
for oil and gas. PPS compositesare used in dynamic and static, high duty cycles, hardened metal running surfaces, and bearing
and wear components for pumps [50]. They are also used as coatings in petrochemical industries because of their outstanding
chemical resistance. Fortron® and Celstran®, sold by Celanese, are high performance pristine PPS and PPS composites used mainly
in oil and natural gas pipelines and pipe fittings as coatings, barrier liners, and structural reinforcements to promote leak-free
environments [52]. The use of PPS helps maintain piping integrity and prevents the release of harmful gaseous and hazardous
substances, which may otherwise cause, not only toxic pollution to the environment, but also unforeseen explosion and fire
accidents. PPS linings also preserves the structure and increases the service life of oil and gas piping systems. Compared to other
commercial pipeline accessories, Fortron® and Celstran® also have the advantages of being resistant to petroleum fluids, sour gas,
hydrocarbons, and paraffin buildup. On the other hand, Chevron Phillips sells, not only Ryton® PPS resin, but also PPS-based alloy
compounds (Ryton® XE Series PPS Alloy Compounds, Ryton® XK Series PPS Alloy Compounds), developed to improve the
ductility of PPS in both injection molding and extrusion grades [53]. RTP Company offers a series of PPS-based resins and
products, which can be used in clean room conveyers, proximity probe housing, and as additives for liquid chemical pump [54].
Given its prominent stability, PPS has been the material of choice for applications like bearings, thrusts, and wear surfaces and
structural components.

Research efforts on PPS are focused on the improvement of its mechanical properties by adding nanofillers, and its adhesion
strength by adding various surface treatments. Stoeffler et al. recently explored the possibility of reinforcing PPS with recycled
carbon fiber [55]. The recycled carbon fibers were recovered by pyrolysis of carbon-fiber- reinforced thermoset composite waste
(Fig. 7). Composites containing 20 and 40 wt% of recycled carbon fibers were produced by compounding with PPS thermoplastic
resin using a twin-screw extruder, followed by injection molding. Although the carbon fibers used are recycled, their mechanical
and physical properties were found to be similar to the aerospace grade virgin carbon fibers. The resulting PPS composites showed
comparable mechanical properties to the equivalent compounds produced using industrial grades of carbon fibers. The flexural
modulus was increased by 530%, the flexural stress at yield by 290–310%, and the impact energy by 250% compared to pure
PPS for the 40 wt% recycled carbon fiber content. There is a 30% decrease in the strain at yield, but the amount of energy to yield is
increased by 170–210% relative to the pure PPS.

The use of volcanic ashes as fillers for PPS has also been explored [56]. Incorporation of volcanic ashes resulted in the increase
in storage and loss modulus of the PPS composites with the loading. This means that as the concentration of volcanic ashes is
increased, the stiffness and energy dissipation ability of the resulting PPS composites are also increased. Thermal stability is also
improved as the volcanic ashes reduce the mobility of the polymeric chains, which results in the lowering of the degree of
molecular motion. Even though the erosion resistance is decreased significantly, the utility of volcanic ashes as fillers may have
economic feasibility. Wang et al., on the other hand, fabricated a self-lubricating PPS by incorporating 1 wt% of zeolite and lithium-
based grease in the pores [57]. The resulting PPS composite showed a friction coefficient of 0.024 and 1.79 × 10-16
m3/Nm wear rate, which are equivalent to 90% reduction in friction coefficient and 4.67 × 104 times increase in wear
resistance, respectively, compared to pure PPS under dry condition.
 Another area of interest is the improvement in adhesion strength of PPS on metal substrates, which is done by thermally
evaporating PPS to form a buffer layer on copper or by employing plasma treatment with reactive gases on the PPS buffer layer [58].
The adhesion strength was increased from ~15 to ~26 MPa, while the samples treated with hydrogen plasma showed ~32 MPa
adhesion strength.

In the past years, there was an exponential growth in the use of additive manufacturing (AM) techniques in fabricating
engineering materials. Polymers represent the majority of the materials available in the market, due to their performance,
versatility, and cost. However, in general, the layer-by-layer fabrication method also results in polymeric parts, which are weaker in
strength compared to the injection-molded parts of the same material [59]. Fitzarhis and coworkers evaluated the effects of printing
temperature and post-processing heat-treatment time on the mechanical properties of 3D printed PPS parts [60]. The temperature-
driven bonding model of roads and layers of the printed parts was explained (Fig. 8a), and it was found that post-processing heat
treatments increased the ultimate tensile strength and Young’s modulus by 80 and 72%, respectively. The properties obtained by
this approach were close to those obtained by compression molding (Fig. 8b). SEM images corroborated the mechanical tests (Fig.
8c), showing that increased heat-treatment temperature led to an increase in inter-road bonding.

Polyetheretherketone.

Polyetheretherketone (PEEK) is a semi-crystalline aromatic polymer having both ether and ketone linkages. PEEK is the most
popular member of the polyaryletherketone family and the first to be fully commercialized. It is generally prepared by
reacting 1,4-benzenediol with 4,4′-difluorobenzenophenone in polar aprotic solvents (e.g. diphenyl sulfone) in the presence
of alkali-metal carbonates. The reac- tion takes place in an inert atmosphere at temperatures approaching the melting point of the
polymer (> 300 ◦C). Table 4 shows the typical properties of PEEKs [61].

PEEK exhibits excellent mechanical and dielectric properties, coupled with outstanding flame resistance and good
chemical resistance. It is also hydrolytically stable and has good wear resistance. All these properties are retained at high
temperatures, which generally make PEEK an excellent polymer for bearings, piston parts, pumps, compressor plate valves,
and cable insulation used in chemical process industries. It is estimated that the market worth of PEEK will be $664 million
(USD) by 2021 [62] due to its emerging use in medical industryas a result of its lightweight and increased biocompatibility. PEEK
is also used in automotive, aerospace, textile, and electrical/electronic applications. However, its high cost and very high molding
and extrusion temperature requirement are the major disadvantages [63].

Currently, PEEK-based materials are used as liners for slicklines, wirelines, drilling jars, and drill pipes in downhole oil and
gas drilling and exploration [64]. PEEK is particularly chosen because of its tensile strength, chemical resistance, ductility, and
thermal stability. PEEK can serve as barrier for protecting metallic structures from corrosive and abrasive fluids, and gases present
during downhole operations. PEEK is also being used as housing for radio frequency identification (RFID) tags for tracking
equipment used during drilling and production of oil and gas wells [65]. PEEK is a preferred choice of material for sealing,
connectors, and valve seats in subsea offshore oil and gas production systems due to its exceptional resistance to harsh conditions
and corrosive environments including the presence of hydrocarbons, hydrogen sulfide, steam, and seawater at elevated
temperatures [66]. In the oil and gas industry, offshore operations are generally riskier compared to onshore activities. Improper
selection of materials for pipe sealants, connectors, wirelines, and the like can lead to oil spills, release of harmful and flammable
gaseous compounds, and other catastrophic incidents which may result in injuries and casualties. VESTAKEEP®, a commercial PEEK
product by Evonik and ideal for use as material of construction for equipment used in subsea exploration, exhibits an excellent
blend of mechanical strength and resistance against varying temperatures and pressures, and weathering conditions [67].
Victrex® sells PEEK polymer products ranging from unfilled, depth-filtered, and glass-filled to carbon-filled and wear-resistant
grades. Solvay, on the other hand, markets KetaSpire® PEEK as one of the highest performing semi- crystalline thermoplastics
available today [68].

Kakinuma et al. improved the anti-bacterial property of PEEK by forming hydroxyapatite film on PEEK substrate and
immobilizing silver ions [69]. The resulting PEEK-based material showed antibacterial activity against S. aureus and E. coli (Fig.
9). The concentration of the immobilized silver ions plays an important role in the cell adhesion and growth. It has been shown
that 5 and 10% silver ions had negative effects, while 0.5 and 1% showed relatively high cell growth compared to the controls.
In vitro analysis of coatings with 0.5 and 1% silver ions showed antibacterial activity without cytotoxicity. The antibacterial
properties are interesting in the context of off-shore operations, where the environmental regulations are usually stricter. Also,
these properties demonstrate that the parts made with this material display desirable levels of chemical stability that are
necessary in such a complex environment. On the other hand, Jung et al. showed that the use of magnesium can also improve
the biocompatibility and resistant to biocorrosion of PEEK. The resulting PEEK material showed excellent mechanical
properties after chemical modification [70].

The use of PEEK as an ion exchange membrane is another field of research interest. Li et al. prepared a membrane comprising of
sulfonated PEEK and sulfonated polyethersulfone-cardo [71]. The Tg and the initial degradation temperature of the resulting
material were 175 ◦C and 310 ◦C, respectively, well-above the typical working temperature ranges for commonly used
membranes. The diffusion coefficient of water was also measured as 10-12 m2 s-1, which is lower compared to 10-10 m2 s-1 for
the commonly used membrane (Nafion®). Similarly, ion exchange membranes can be prepared by radiation-induced grafting of
alpha methyl styrene-butyl acrylate mixture onto PEEK films and subsequent sulfonation, or by mixing sulfonated PEEK and
fluorinated polyimide [72,73]. PEEK can also be used in electromagnetic interference (EMI) shielding applications by mixing
expanded graphite [74]. The electrical conductivity threshold was found to be 1.5 wt%, and the resulting electrical conductivity is
eleven orders of magnitude higher than that of the pristine PEEK. An EMI shielding effectiveness of up to 58 dB for the
resulting nanocomposites can be obtained.
 Liquid crystalline polymers.

Liquid crystalline polymers (LCPs) are partially crystalline aromatic polyesters based on p-hydroxybenzoic acid and similar
monomers. They exhibit highly ordered structures both in melt and in solid states. LCPs can be categorized as lyotropic (i.e.
crystallinity occurs when the polymer is dissolved in a solvent) or thermotropic (i.e. crystallinity occurs when the polymer is heated
above its Tg or melting temperature). The most popular example of lyotropic LCP is the commercially available aramid known as
Kevlar. First developed by DuPont in the 1960s, Kevlar is an aromatic polyamide that derives its exceptional mechanical strength
from the many intermolecular hydrogen bonds between the carbonyl groups and the N–H centers. Additional strength is brought
about by the aromatic stacking between adjacent strands [14]. Its lightweight, heat resistance, and exceptionally high tensile
strength makes Kevlar a preferred choice of material for personal protective equipment (PPE) for workers in the oil and gas
industry. Unlike those made of leather and nylon, PPEs such as sleeves, gloves, and hard hats made of Kevlar not only provide
comfort to the wearer, but also the highest level of protection against thermal and fire exposure, hazardous and flammable
chemicals, and mechanical and other multiple hazard risks [75]. Kevlar is also used as reinforcement for offshore pipeline risers that
transport oil from the ocean floor up to the surface. On the other hand, the most popular thermotropic LCP is Vectran (first
developed by Celanese and currently manufactured by Kuraray), an aromatic polyester produced by the polycondensation of 4-
hydroxyben- zoic acid and 6-hydroxynaphthalene-2-carboxylic acid [76]. Due to its stiffness and strength, spun and woven Vectran
fibers are used in oil and gas offshore units as mooring and sensor cables, umbilicals, and ropes for deep water lifting with no
stretch required. These material mechanical characteristics are desirable during such operations in order to prevent parting of
ropes or cables, which may injure or even kill a worker. Typical properties of LCPs are shown in Table 5 [77].

LCPs exhibit outstanding mechanical strength at very high temperatures, and excellent resistance against chemicals, weathering
conditions, radiation, and burn. These properties make LCPs a very good candidate for replacing metals, ceramics, composites, and
other high performance polymers as engineering parts, automotive electronics, appliances, connectors, bobbins, and even food
containers. Although there are a number of LCPs that have been produced in the 1970s, it was not until 1984 when LCPs became
commercially available. Although LCPs have thermo-mechanical properties that are superior to some HPPs, it still suffers from a
few disadvantages. Some of which include high cost, highly anisotropic properties, ability to form weak weld lines, and dry
condition requirement prior to processing [78].

Recently, there is an immense research interest on incorporation of nanomaterials in LCPs to further enhance their properties.
Reis et al. incorporated nanoclay into Kevlar/epoxy laminates to enhance their impact resistance [79]. Specifically, Nanoclays
Cloisite 30B was dispersed in Kevlar/epoxy composite. Increasing the amount of nanoclay led to an increase in the maximum
impact load for the resulting polymer nanocomposite. Graphene-nanoribbons have also been used as nanofillers to reinforce
polymers like PVC and PMMA [80]. The dispersion was improved by functionalizing the graphene-nanoribbons with Kevlar prior to
mixing with the polymer matrix. The Young’s modulus of PVC with Kevlar-functionalized graphene-nanoribbons reaches a
maximum of 2.36 GPa, while its yield strength reaches a maximum of 81.11 MPa. These values are equivalent to ~72.3 and
106% increase, respectively, relative to the pristine PVC. Similarly, the Young’s modulus and the yield strength of PMMA with
Kevlar- functionalized graphene-nanoribbons showed 127 and 144% increase, respectively, relative to pure PMMA.

Similar studies were done using Kevlar nanofiber-functionalized multiwalled CNTs to reinforce poly(vinyl alcohol) and
PMMA [81]. There is also an interest in understanding the effects of hydrolytic aging on Kevlar/epoxy and glass/Kevlar/epoxy
composites [82]. It has been shown that the moisture uptake when Kevlar/epoxy is immersed in sea water is higher than that of the
glass/epoxy composites due to the presence of aramid fibers. Water absorption results in a significant decrease in tensile and
flexural properties of the composites because of the degradation of the fiber matrix interface. Lastly, there is also some interest
in the use of LCPs as radiation shields [83]. In general, highly hydrogenated materials like polyethylene show high radiation
shielding properties. Recently, it was shown that Kevlar had similar shielding behavior property and was also known to have debris
shielding, which is ideal for use as space suits. During drilling operations, different radiation techniques are used for well
logging, therefore, HPPs and their composites with shielding properties are useful in preventing degradation or interference on the
performance of equipment and parts that are vital for the operation [84]. The replacement of these items can considerably increase
the time and cost of drilling operations, making it necessary to effectively design materials to enable quick and safe drilling [85].

Structural polymeric materials are prone to cracking, which are difficult to detect and repair. These cracks can lead to
mechanical degradation, electrical failure, loss of adhesion, etc. [86]. In this context, self-healing materials emerge as a convenient
solution to extend the lifetime and performance of parts, especially in complex environments found in the oil and gas industry. Yan
and coworkers synthesized liquid crystalline block copolymers (LCBC) by reversible addition-fragmentation chain transfer
polymerization (RAFT), consisting of a side-chain liquid crystalline polymer and a soft segment with multiple hydrogen bonds [87].
Viscoelastic properties of the LCBCs investigated by dynamic mechanical analysis (DMA) indicated that the material showed
rubber-like features at room temperature. The self-healing properties of the material was also evaluated. Initially, the material
was cut in two completely separate pieces at room temperature (Fig. 10a). The parts were then brought together and
heated at 50 ◦C (Fig. 10 b-d). The material spontaneously self-healed over time and no fracture could be visually identified after 10
min. Scattering and diffraction experiments revealed that intermolecular hydrogen bonding played a very important role in
microphase separation of the LCBC, being favored at higher temperatures, which led to the self-healing phenomenon (Fig. 10e).

Other high performing polymers

Fluropolymers.

Fluoropolymers are characterized by chemical structures primarily consisting of C–F bonds, or copolymers prepared from
fluorine-containing monomers. These polymers are particularly important because of their outstanding chemical inertness
brought about by the presence of very electronegative fluorine atoms. Fluoropolymers neither readily interact nor bond with
other materials; this behavior is usually referred to as being water-repellent or nonstick [88,89]. Aside from chemical
inertness, fluoropolymers are well-known for having high- temperature resistance due to their high dissociation energy of
C–F bond (123 kcal mol-1) and semi-crystallinity in nature. There are a number of industrially relevant fluoropolymers such
as polytetra-fluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene tetrafluoroethylene copolymer (ETFE),
fluorinated ethylene propylene (FEP), polyvinyledene fluoride (PVDF), and perfluoroalkoxy (PFA). The thermal stability and
chemical inertness of fluoropolymers depend on the degree of fluorination: fully fluorinated polymers (e.g. PTFE) are resistant to
a wider range of chemicals than partially fluorinated polymers (e.g. PCTFE). However, fully fluorinated polymers display weaker
mechanical properties (tensile strength, toughness, abrasion, and cut- through resistance) than those for partially fluorinated
polymers at ambient temperature. Typical properties of fluoropolymers are shown in Table 6 [90].

Aside from outstanding chemical inertness and mechanical strength, fluoropolymers are also known to have good weather
resistance, good flexibility, good electrical properties, and low friction. They have been used to make seals, gaskets, tubing, valve
parts, coatings, and hose. PTFE, in particular, is used in wire and cable insulation for electrical/ electronic applications; plumbing
and fluid processing equipment for petroleum, chemical, and medical applications; textile fibers for clothing, dental floss, and
industrial applications; lubricants for print- ing; cookware coatings; and coating and lubrication applications for vehicles, building
constructions, and appliances [94]. Fluoropolymers, however, are very difficult to process, and may produce hazardous
decomposition products [95].

In the oil and gas industry, fluoropolymers are mainly used as linings and protective coatings for metallic equipment and pipes
to prevent corrosion and contamination of oil products. Their main advantages over other polymers are their low coefficient of
friction, nonstick property, chemical inertness, high thermal stability, and low surface energy [84]. Thus, fluoropolymer coatings are
hydrophobic in nature and can reduce the deposition of organic and inorganic scales (e.g. BaSO4 and CaCO3) in production
tubular and specifically minimize asphaltene deposition and precipitation in reservoirs and pipelines during oil production [96,97]
Because of their superior protective properties, fluoropolymer coatings [88] are essentially the choice of material for metal
protection against aggressive chemicals, mechanical abrasion, wear and tear, and high-temperature environments, all of which, if
not circumvented, may result in catastrophic corrosion-related accidents. Fluoropolymers have also been used as sealants and O-
rings. DuPont is a leading producer of fluoropolymers with Teflon® (PTFE) as their most popular product. Because of its high
temperature tolerance, Teflon® is ideal for jacketing, insulation, and coatings for high- temperature operating equipment in oil and
gas (e.g. heat exchangers) [98]. It is noteworthy that improper selection of coating materials for heat exchanging equipment
may reduce the effectiveness of heat transfer process and cause surface erosion and fouling. DuPont also sells Tefzel® (ETFE),
with combined mechanical toughness and outstanding chemical inertness [99]. Solvay also sells fluoropolymer products including
Halar® ECTFE, a copolymer of ethylene and chlorotrifluoro- ethylene, and Hyflon® PFA and MFA®, both semicrystalline and fully-
fluorinated melt processable fluoropolymers [15].

Current research efforts are geared toward understanding the structure-property relationship for further improvement on the
mechanical performance and protective action of fluoropolymers against abrasion and harsh environment. Saffarini et al. evaluated
the wetting behavior of three 0.2-μm commercial expanded PTFE membranes under membrane distillation conditions [100].
Results showed that increase in temperature led to the relaxation of the internal stresses in the fibrils of the PTFE membrane. As a
consequence, a temperature-dependent geometric correction factor in the Laplace (Cantor) formulation of liquid entry pressure
estimation is recommended to predict the wetting of PTFE membranes under non-isothermal conditions.

Also, there is a growing interest in understanding how nanofillers can improve the wear resistance of PTFE. Ye et al. used
uninterrupted microscopy measurements to study the evolution of transfer film development for an ultra-low wear PTFE
nanocomposite [101]. It was observed that the detectible debris vanished and the wear rates approached zero, both of which are
due to the transfer of nanoscale and oxidized fragments of PTFE on the counterface. The study further revealed a complex interplay
among the elements of transfer film adhesion, chemistry, debris morphology, and mechanics in the wear of PTFE nanocomposites.
When fluoropolymers are subject to extreme temperatures, thermal decomposition fragments are produced. Myers et al. used
ultrahigh-resolution mass spectrometry and mass defect filtering to identify the thermal decomposition products, which could
environmentally be persistent and toxic [102]. With these techniques, 29 perhalogenated carboxylic acid and 21
chlorine/fluorine substituted polycyclic aromatic hydrocarbon congener classes of thermal decomposition products of PCTFE have
been identified.

Superhydrophobic coatings have gained a lot of attention in the past years due to their wide range of applications in the oil and
gas industry: anticorrosion, self-cleaning, anti-icing, and oil/water separation [89,103–108]. Recently, Matin, Baig and Gondal
prepared a super- hydrophobic coating based on perfluorooctyltrichlorosilane (PFOTCS) on a stainless steel mesh screen (Fig.
11a,b) [109]. Mesh screens coated with superhydrophobic coatings are well-known effective strategy foroil/water separation, since
they prevent the passage of water, but selectively allow oil to pass through them. The uncoated membrane allowed the
water/hexadecane (50/50 v/v) mixture to pass thought it (Fig. 11c), while the membrane with a superhydrophobic coating effi-
ciently separated water from hexadecane. As shown in Fig. 11d, water stayed on the upper part of the experimental setup, while
hexadecane was collected at the bottom. Different superhydrophobic coatings used fluorosilanes to enhance the adhesion with the
substrate and increasethe water repellency [110,111].

Thermosetting epoxy.

Epoxy resins or polyepoxides are a class of polymers that contain epoxide reactive end-groups, which can react with each
other with the aid of a catalyst (catalytic homopolymerization), or co-reactant (also known as hardeners or curatives). Typical
co-reactants are polyamines, phenols, alcohols, thiols, and acid anhydrides [14]. Upon curing, the epoxy resin forms a
thermoset that cannot be further melt processed. The resulting cured material, however, displays excellent chemical
resistance, high heat resistance, high strength, and good corrosion resistance. Typical properties of epoxy are shown in Table
7 [112].

Since their introduction in the 1950s, epoxy resins have found ap- plications as adhesives, laminates, anti-corrosion coatings,
bonding agents, molds, electrical parts, and are indispensable polymeric mate- rials in automotive and military applications.
Epoxy, however, exhibits poor oxidative stability and is chemically sensitive to moisture. Moreover, their thermal stability is
only limited to up to 177–232 ◦C and their specialty grade forms can be very expensive [113].

Epoxy resins have been dubbed as the most popular family of high performance thermosetting materials. Specifically, their
multifunctional (i.e. with 2 epoxide groups) and toughened versions have been recognized as the most important thermosetting
epoxy matrices for a wide range of industrial products including high performance coating materials and carbon fiber composites
[114–117]. Due to their adhesive strength, epoxies have become the preferred choice of material for ad- hesives and coatings for
pipes, valves, fittings, girth welds, and rehabilitation of existing pipelines in the oil and gas industry. Similar to fluoropolymers,
multifunctional epoxies are well-known for their excellent protection performance [114,115] against corrosion, high heat, and
pressurized environments, particularly during offshore drilling activities. When mixed with amine, the epoxy coating is used for
grouting and sealing purposes on pipelines prior to installation of repair or reinforcing of sleeves or clamps. Industrial grade high
performance epoxy polyamine coatings, sold by Sherwin-Williams, are used in a variety of industrial maintenance and high
performance applications because of their extremely high chemical, impact, wear, and abrasion resistance [118]. Epoxy-based
novolac (phenol-formaldehyde-based) vinyl esters, in which the methacrylate copolymerizes with styrene upon curing, are high
thermal performance densely crosslinked materials, which can be used in downhole oil and gas production as coatings and sealants
[119]. When reacted with polyurethane (PU), a high performance interpenetrating polymer network (IPN) material is
obtained with enhanced thermal resistance and mechanical properties [120]. Epoxy/PU IPNs have been used to coat girth welds,
ballast tanks, ships, and marine structures. It has also been used as exterior coating for buried or immersed pipelines [121].

Polymers of plant origin or produced from other renewable sources have been widely investigated for use in the petroleum
industry [122–125]. Given the wide range of applications of epoxy and the growing need for environment-friendly materials, there
is an immense interest in studying bio-based epoxy, which aims to replace its petrochemical counterparts. Li et al. compared the
properties between rosin- based epoxy and benzylamine-based epoxy [71]. Results showed that the bio-based epoxy had lower
curing reactivity brought about by its bulky pendant group, leading to a higher curing temperature. It was also observed that the
bio-based epoxy had a higher Tg, but weaker tensile and flexural properties. Sasaki and coworkers used lignin extracted from
steam-exploded bamboo as a resource material for the production of cured epoxy resins [126]. The thermal and mechanical
properties of the lignin-based and the petroleum-based epoxy resins were compared. Although the lignin-based epoxy
exceeded the dip-solder resistance test (250–280 ◦C), it only had 70% of the flexural strength of the petroleum- based epoxy
resin. Aouf et al. synthesized a novel bio-based epoxy from gallic acid, which is a phenolic resin extracted from various plants
[127]. The resulting epoxy showed high Tg and crosslinking density.

Nguyen and coworkers [124] developed bio-based epoxy networks from a cardanol-derived prepolymer (CA) and two different
phosphonium-based ionic liquids (ILs) (Fig. 12a), as well as with an aliphatic diamine (Jeffamine® D230). They also studied
the incorporation of the bio-based CA in a conventional epoxy prepolymer, bisphenol A diglycidyl ether (DGEBA), with the
same curing agents (D230 or ILs). CA/IL networks were processed with excellent thermal stability, good thermo-mechanical
properties combined with high hydrophobicity, thanks to the unique structure of the cardanol-based epoxy prepolymer.
Particularly, the ILs led to a significant improve- ment in the thermal stability (> 460 ◦C) of the CA-based networks (Fig.
12b). Finally, the incorporation of CA combined with the chemical nature of the phosphonium ILs plays a key role in the
properties of modified epoxy networks, especially on the fracture toughness and surface energy. This work opened a new way to
developing sustainable materials, which can outperform the petroleum-based materials. A overed the advances in bio-based
epoxy resins and bio-based curing agents [128].

Polyurethanes.

Polyurethanes (PUs) include polymers that are produced by the reaction of organic isocyanate and compounds containing
hydroxyl groups. Depending on the starting monomer, PUs can be designed to be a thermoset or a thermoplastic, rigid and hard,
or flexible and soft, and solid or foamy [129]. Typical properties of Pus are shown in Table 8 [130].

Rigid PUs have been used as insulation materials because of their low heat transfer and high electrical resistance. PUs have also
been used in offshore applications, such as the vortex-induced vibration (VIV) strakes, wherein spiral sheaths made of PUs are
affixed to the pipeline. The helical shape of the strake allows the vertical dissipation of horizontal current forces. [48] Aromatic
PUs, however, have inferior light stability. When an aromatic PU is exposed to light, it discolors from off- white to reddish brown.
Although it is a drastic color change, it has been reported that the bulk property of the PU is maintained. PUs are also ions
susceptible to chloride attack, particularly in HCl and H that convert PUs into amine salts and polyols [129].

PUs have been reformulated and modified into their functionalized and/or crosslinked forms for utility in the fabrication of
high perfor- mance coatings [131], elastomers [132], and carbon fiber composites [133]. In the oil and gas industry, similar to
fluoropolymers and epoxies, high performance PUs have been generally used as coatings for ship hulls, rudders, marine pilings,
docks, and ballast tanks, and protection of offshore structures and hydraulic fracturing (or fracking) equipment such as slurry
blender and fracturing pumps [7]. Fracking is a generally known risky activity during oil and gas drilling and use of low-quality
coating materials may lead to unnoticeable equipment damage and further breakdown, causing sudden accidents or other
serious safety- related incidents. PUs have also been used to coat pipes, valves, fittings, girth welds, and in rehabilitation of
existing pipelines [134]. PUs have been used as linings for gondola railcars, tanks, and sewage digesters.

The current research on PUs relevant to the oil and gas industry focuses on the inclusion of various nanomaterials for overall
property enhancement. Liao et al. incorporated aqueous reduced graphene into PU matrix to prevent the aggregation and stacking
of graphene upon reduction and evaporation of water [135]. The fabricated aqueous reduced graphene/PU nanocomposite showed
improved electrical and mechanical properties compared to the pristine PU. The properties were even comparable to the properties
of thermally reduced graphene/PU nanocomposites. Aqueous reduction of graphene is a low energy process and does not require
hazardous chemicals. Thus, it is found to be a more environmentally sound approach to producing graphene.

The incorporation of nanofillers into PU is expected to further enhance its mechanical and barrier properties. According to Xiang
and coworkers [136], incorporating hexadecyl-functionalized low-defect graphene nanoribbons into PU improves its gas barrier
properties (Fig. 13). The nitrogen gas diffusivity of PU was decreased by three orders of magnitude after loading 0.5 wt% graphene
nanoribbons. Additionally, Yao et al. showed that a new type of piezoresistive sensor with ultrahigh pressure sensitivity can be
fabricated using a fractured microstructure design in a graphene-nanosheet-wrapped PU sponge [137]. Results revealed that the
sensor can detect up to 9 Pa of pressure.

HPPs in additive manufacturing.

In recent years, additive manufacturing (AM), commonly known as 3D printing, has been increasingly applied in the oil and gas
industry. A wide variety of different printing techniques have been developed, including fused deposition modeling (FDM),
stereolithography (SLA), selective laser sintering (SLS), direct ink writing (DIW), etc. These techniques are all based on a layer-by-
layer deposition process, where one layer of feeding material is patterned first, followed by subsequent layer deposited onto the
previous layer, and a 3D object is fabricated by stacking the layers together, as shown in Fig. 14 [138,139]. This unique fabrication
process offers many potential benefits that are very useful in the oil and gas industry. The fast prototyping offered by AM helps to
expedite the product development process by avoiding the time- consuming and expensive machining and tooling process
[140,141]. For example, GE oil and gas has used AM to produce the burner for a NovaLT16 gas turbine, which significantly reduced
the time for concepts design and validation testing, and saved more than 50% of the cost. Besides, the AM provides more significant
impact on the supply chain management for oil and gas industry [141]. The oil and gas assets are being deployed in increasingly
more isolated locations, in which the repair and replacement of fault parts becomes a costly issue due to the short life-cycle of some
components, obsolete parts, and small number productions. With the advantage of AM, these parts can be digitally scanned, reverse-
engineered, and additively manufactured on the fly, which offers high flexibility and just-in-time production of the critical
components.

HPPs are among the key materials used in AM for oil and gas. The lightweight and high strength, excellent thermal and
chemical resistance enable HPPs to be used as key components, such as downhole tools, completions tools packers, etc. The
development of 3D printing of HPPs in recent years additionally affords cost saving, lead time reduction, and better supply chain
management, as discussed above. Numerous HPPs have been successfully 3D printed. Thermoplastic polymers, such as PEEK,
PPSU, and ULTEM have been reported to be printed by FDM, of which high nozzle temperature above 350 ◦C is required
to melt and extrude the polymer, high bed temperature above 100 ◦C is required to ensure strong bed adhesion, and high chamber
temperature above 60 ◦C is required to prevent severe warping [138]. SLS printing of PEEK has also been reported, which offers
better geometry complexity, although with a higher cost [142]. Thermoset HPPs, such as bisphenol A based epoxy resins, epoxy
composites, poly-benzoxazines, etc. have been reported to be successfully printed by direct ink writing. The rheology of the
liquid or solid monomers were first modified by addition of inorganic fillers to reach a thixotropic state, and the complete thermal
curing was conducted upon the post-printing process [143]. SLA has also been used in HPP fabrications. For example, epoxide resins
have been blended with acrylate-functionalized materials that render good UV curability [144]. The development of printing
techniques as well as the formulation of new polymer resins that are suitable for various printing techniques are being intensively
studied.The HPP 3D printing thus holds a huge potential to be used in a wide range of applications in the oil and gas industry.

Conclusion

In this review article, we discussed a variety of HPPs and their potential applications particularly in the oil and gas industry. The
structure-property relationships of commonly used HPPs have been discussed, as well as current research efforts on these
polymers. Depending on the desired material property, there is a specialized kind of polymer that can be used with or without
additives in order to enhance the material safety, durability, and performance. Although the oil and gas industry presents a wide
range of opportunities for HPPs, the complex environments (high temperature, high pressure, high salinity, etc.) may impose many
technical challenges. The improvement on the HPP properties, use of AM in manufacturing, and expansion on the number of
applications are currently being investigated by many materials scientists worldwide.
Fig. 1. (a) NDK Crystal damage after the incident. The exterior wall panels were blown out because of the force of the explosion. (b)
Aerial photo of explosionfragment locations and distance from the facility [4].

Fig. 2. Images of the (a) ruptured riverside hose, (b) flow restricted hillside hose, and (c) a new hose with attached ID tag [5].
Fig. 3. Hierarchy of Polymer materials according to their temperature, chemical, and mechanical stability.
Fig. 4. Representation of the intermolecular interactions between the components of (a) PSU/PAI and (b) PSU/PAI/TiO2 blend membranes. Effect of PAI con-
centration on the humic acid rejection and humid acid permeation of PSU/PAI/TiO2 nanoparticles (cirle: without TiO2; triangle: with TiO2) [33].
 Fig. 5. Schematic representation of the carbon nanotube with silver nanoparticles that is later
incorporated in PEI [47].

Fig. 6. (a) Schematic illustration of the PDA/PEI coating deposition on a magnesium alloy. AFM images of the (b) Mg substrate, (c) PDA-
coated and (d) PDA/PEI-coated substrates [48].
Fig. 7. Before and after pyrolysis of (a) epoxy and bismaleimide prepregs, and (b) finished parts [55].
Fig. 8. (a) The bonding process in AM. (b) Stess-strain curves for the printed and compression molded PPS dogbones. (c) SEM cross section images of the PPS parts at
different temperatures [60].
Fig. 9. Halo test of (A) S. aureus, and (B) E. coli on PEEK functionalized with hydroxyapatite and silver ions. [69]

10
Fig. 10. Self-healing test: (a) the material was completely cut in half at room temperature, and both sides were brought together and heated at 50 ◦C for (b) 5, (c) 10,
and (d) 20 min. (e) Aggregation morphology and self-healing mechanism of LCBCs [87].
Table 6
Typical properties of fluoropolymers [90].
Physical Nominal Value Unit Test Method

Specific Gravity 1.80 to 1.90 ASTM D792 [17]

Mechanical Nominal Value Unit Test Method
Tensile Strength (Yield, 23 ◦C) 12 to 22 MPa ASTM D638 [20]
Tensile Strength (Break, 23 ◦C) 7 to 25 MPa ASTM D638 [20]
Tensile Elongation (Break, 23 ◦C) 180 to 330% ASTM D412 [91]
Tear Strength (23 ◦C) 0.8 to 1 MPa ASTM D624 [92]
Thermal Nominal Value Unit Test Method
Brittleness Temperature -26 to -17 ◦C ASTM D746 [93]
Melting Temperature 120 to 222 ◦C
Fig. 11. Scheme of the (a) hydrolysis and (b) polycondensation reactions occurring at the membrane-silane interface that result in the bonding of the PFOTCS
molecule to the surface and formation of siloxane network. Photographs of the water/oil separation experiment for the (c) uncoated and (d) coated mem- branes
[109].
Fig. 12. (a) Chemical structures of Cardolite, a cardanol derived epoxy prepolymer and two phosphonium ILs. (b) TGA/DTG curves for the biobased epoxy networks
with different ILs [124].
Fig. 13. (a) Representation and (b) SEM image of a thermoplastic polyurethane composite film containing hexadecyl-functionalized low-defect graphene nano-
ribbons [136].

Fig. 14. Schematic illustration of layer-by-layer deposition process in various 3D printing techniques. a) Fused deposition modeling. b) Stereolithography. c) Se-
lective laser sintering.
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